Production of polycyclic compounds



United States Patent 3 258 501 PRODUCTION OF PhLYcYcuc COMPOUNDSLawrence G. Cannell, Lafayette, Califi, assignor to Shell Oil Company,New York, N.Y., a corporation of Delaware No Drawing. Filed Mar. 3!),1964, Ser. No. 355,889 6 Claims. (Cl. 260-666) This invention relates toa novel class of polycyclic organic compounds and to methods for theproduction thereof. More particularly, it relates to novel saturated andethylenically unsaturated tricyclo(4.2.1.0 hydrocarbons containing aring system of 9 carbon atoms, and the methods by which such polycycliccompounds are produced.

It is an object of the present invention to provide a novel class ofpolycarbocyclic organic compounds and methods for the productionthereof. More particularly, it is an object of the present invention toprepare novel hydrocarbons containing a tricyclo(4.2.1.O carbocyclicring system, which ring system is saturated or contains from 1 to 2ethylenic linkages wherein no bridgehead carbon atom is a member of anethylenic carboncarbon bond. An additional object is to provide novelmethods for the production of such tricyclic compounds.

It has now been found that these objects are accomplished by processeswhich comprise the condensation of unsaturated bicyclic ring systemswith certain other unsaturated molecules in the presence of transitionmetal complexes as catalysts. Such condensation processes provide thedesired ring system directly, or alternatively provide precursorsthereof, from which compounds incorpo rating the desired ring system areeasily obtained.

The novel compounds of the invention comprise the tricyclo(4.2.l.0)nonanes and the corresponding ethylenically unsaturated tricycliccompounds having from 1 to 2 endo ethylenic linkages, i.e., non-aromaticcarboncarbon double bonds, wherein both carbon atoms are members of thecarbocyclic ring system. Generically, these compounds are nontodi-ethylenically unsaturated tricyclo(4.2.l.0 )nonanes. Althoughnumerous position isomers are available when the tricyclic compoundcontains ethylenic linkage(s), preferred compounds of the invention arethose nonto di-ethylenically unsaturated tricyclo(4.2.1.0 )nonaneswherein no bridgehead carbon atom, i.e., no carbon atom common to two ormore rings, is a member of an ethylenic linkage. One class of suchcompounds has from 9 to 89 carbon atoms, preferably from 9 to 40, and isrepresented by the formula l I I RI R n wherein R and R independentlyare hydrocarbon containing no nonaromatic unsaturation, e.g., alkyl,cycloalkyl and aryl, having from 1 to 10 carbon atoms, preferably from 1to 6; m represents the number of R groups and is a whole number from 0to 6 inclusive and n is a whole number from 0 to 1 inclusiverepresenting the number of R groups. In the above-depicted formula, thedotted line designation is employed to indicate possible locations ofethylenic linkages. The designation, as employed herein, genericallysignifies that the bond between the carbon atoms connected by the dottedline may be a single bond, i.e., a saturated carbon-carbon linkage, oralternatively may be a double bond, i.e., an

ethylenic linkage, depending, of course, on whether the polycycliccompound is saturated, mono-ethylenically unsaturated ordi-ethylenically unsaturated. It will be appreciated that in accord withthe preference for tricyclic compounds which are saturated orunsaturated with endo ethylenic linkages not involving bridgehead carbonatoms, the locations designated by the dotted lines are the onlycarbon-carbon bonds which may alternatively be single or double bondsdepending upon the degree of ethylenic unsaturation in the molecule. Itshould be understood that in the above-depicted formula, R and R groupsreplace hydrogen substituents on the corresponding unsubstituted nontodi-ethylenically unsaturated tricyclo(4.2.l.0 nonane. Preferredcompounds of the above-depicted formula have only a single substituenton any one carbon atom of the eight-membered ring, and most preferredare the compounds wherein the 2 and 5 carbon atoms possess hydrogensubstituents.

The tricyclic compounds of the invention are produced by alternatemethods. Each method, however, involves the condensation of a bicycliccompound with an unsaturated molecule in the presence of a transitionmetal complex as catalyst. Suitable catalysts are complexes oftransition metals of Group VIII of the Periodic Table, particularlynickel, wherein the metal is present in a reduced oxidation state and iscomplexed with stabilizing ligands. By stabilizing ligand is meant aligand capable of donating an electron pair to form a coordinate bondwith the metal, and simultaneously having the ability to acceptelectrons from the metal, thereby imparting stability to the resultingcomplex. Examples of such stabilizing ligands are carbon monoxide;compounds containing conjugated unsaturation such as acrylonitrile,methyl vinyl ketone and acrolein; cyclic polyolefins such as1,5-cyclooctadiene and bicyc1o(2.2.1)hepta-2,5-diene; acetylenes such asZ-butyne and phenylacetylene; trisubstituted derivatives of trivalentmembers of Group V of the Periodic Table, such as the phosphines,phosphites, stibines and arsines; and the like.- Suitable nickel complexcatalysts are those wherein the nickel is present in a reducedoxidation'state, e.g., +1 or lower, and preferred catalysts containnickel in a zero oxidation state complexed with stabilizing ligands.Although nickel complexes such as tetrakis(trialkylphosphine)nickel (0),

tetrakis(triarylarsine)nickel (0), tetrakis(triarylphosphine)nickel (0)and bis(trialkylstibine)nickel (0) dicarbonyl are satisfactory, bestresults are obtained when the catalyst is atetrakis(trihydrocarbylphosphite)nickel (0) complex. formula [P(OR") Niwherein R" independently is hydrocarbyl having from 1 to 10 carbonatoms, as illustrated by alkyl R groups such as methyl, ethyl, propyl,sec-butyl, amyl, iso-amyl, hexyl, octyl, Z-ethylhexyl, decyl, benzyl and,B-phenylethyl; cycloalkyl R" groups including cyclopentyl andcyclohexyl; and aryl R" groups such as phenyl, tolyl, xylyl, ethylphenyland p-tert-butylphenyl. Preferred R" groups are free from non-aromaticunsaturation, and in general, acyclic alkyl groups are preferred overcycloalkyl and aryl substituents in the phosphite ligands of thecatalyst.

Exemplary tetrakis (trihydrocarbylphosphite)nickel (0) 10 catalystsinclude Tetrakis (tributylphosphite nickel O) Tetrakistriphenylphosphite) nickel 0) Tetrakis (tripropylphosphite nickel (0)Bis (tritolylphosphite bis (trihexylphosphi-te nickel (0 Tetrakis(amyldibutylphosphite)nickel (0) and the like. Particularly useful ascatalyst is tetrakis[tri- (2-ethylhexyl)phosphite]nickel (0). The nickel(0) catalysts are conveniently prepared by any of several methods, e.g.,according to the disclosure of US. 3,102,899 issued September 3, 1963,to Cannell, or the disclosure of copending application of Mullineaux,Serial No. 275,517, filed April 25, 1963.

Such catalysts are represented by the' The nickel complex catalysts arepreferably employed as preformed materials but alternatively may beprepared in situ, as by the reaction of a nickel (I) or nickel (11)compound with a suitable reducing agent. For example, nickel (II)acetylacetonate reacts with triethyl aluminum in the presence oftriphenylphosphine and the reactants at temperatures from about 20 C. toabout 20 C. to afford a nickel (0) catalyst.

In one modification of the process of the invention, the tricycliccompounds are produced by the dimerization of abicyclo(2.2.1)hepta-2,5-diene in the presence of the preferred nickel(0) complex catalyst, followed by pyrolysis of the product therebyproduced. The bicyclo(2.2.1)- hepta-2,5-diene is conveniently preparedfrom a cyclopentadiene and an acetylene such as by the process describedin US. 2,875,256 issued February 24, 1959, to Hyman et al.

By the choice of appropriately substituted cyclopentadienes andacetylenes, bicyclo(2.2.l)hepta-2,5-dienes containing variedsubstituents may be produced, for example, from2,3-dimethylcyclopentadiene and acetylene is produced 2,3dimethylbicyclo(2.2.1)hepta 2,5-diene. Preferredbicyclo(2.2.1)hepta-2,5-dienes are those wherein any ring substituentsare hydrocarbyl, and from consideration of subsequent process steps, itis preferred that at least one pair of carbon atoms connected by anethylenic linkage have hydrogen substituents. Such preferredbicycloheptadienes are represented by the formula R wherein R and m havethe previously stated significance. Subsequent to the dimerizationprocess, the pentacyclotetradecadienes are thermally converted to areaction mixture containing the desired tricyclononadiene, abicyclononatriene byproduct that is isomeric therewith, andcyclopentadiene in an amount equimolar with the total of the polycycliccompounds. This conversion is illustrated by the equation below whereinR and m have the previously stated significance.

The thermal conversion of pyrolysis of the pentacyclo tetradecadiene isconducted in a batchwise manner, as by maintaining the reactant at anelevated temperature and removing the pyrolysis products therefrom as bydistillation, or alternatively the pyrolysis is conducted in acontinuous manner as by passing the pentacyclotetradecadiene through aheated tube and recovering the desired product from the eflluent. Itwill be appreciated that although the above formula represents a planarconfiguration, various endo and exo isomers of thepentacyclotetradecadiene are formed during bicycloheptadienedimerization and the ease of pyrolysis of the isomers will be somewhatvariable. Pyrolysis temperatures above about 200 C. are generallysatisfactory, although it is desirable to avoid pyrolysis temperaturesabove about 525 C., in part because of the significant amounts ofbyproducts, e.g., allylbenzene and indene, obtained by the rearrangementof the polycyclic reactant when such higher temperatures are employed.Best results are obtained when pyrolysis temperatures from about 250 C.to about 450 C. are utilized. The pyrolysis may be conducted atpressures that are atmospheric, subatmospheric or superatmospheric.Little advantage is gained by the use of pressures other thanatmospheric, and utilization of pressures that are substantiallyatmospheric is preferred.

The ratio of the polycyclic products obtained by pyrolysis is somewhatdetermined by the reaction conditions, particularly the pyrolysistemperature and the residence time, that are employed. At reactiontemperatures below about 300 C., the molar ratio of tricyclononadiene tobicyclononatriene is about 7:1. At higher temperatures, the relativeproportion of bicyclotriene increases, probably because of isomerizationof the tricyclononadiene under the more vigorous conditions.(4.2.1)nona-2,4,7-triene and derivatives thereof is described more fullyand is claimed in co-pending application of L. G. Cannell, filed of evendate.

Subsequent to the pyrolysis reaction, the products are separated andrecovered by conventional methods such as fractional distillation,selective extraction and the like.

An alternate method for the production of the novel tricyclic compoundsof the invention comprises the reaction of a monoto di-ethylenicallyunsaturated bicyclo (2.2.1)heptane with an acetylenic hydrocarbon in thepres ence of the nickel (0) complex as catalyst. The acetylenichydrocarbon comprises a carbon-carbon triple bond wherein the carbonatoms there-of are substituted with hydrogen or hydrocarbyl radicalswhich contain no non- .aromatic unsaturation. Preferred acetylenichydrocarbons are represented by the formula R CER' wherein R and n havethe previously stated significance. It will be understood that wheneither It is 0, the remaining valence of the carbon atom(s) will becompleted by combination with hydrogen atom(s). The acetylenichydrocarbons are mono-alkynes having from 2 to 22 carbon atoms,preferably from 2 to 14.

The acetylenic hydrocarbon is reacted with a monoto di-ethylenicallyunsaturated bicyclo(2.2.1)heptane wherein no bridgehead carbon atom is amember of an ethylenic linkage, and wherein the carbon atoms of at leastone ethylenic linkage is substituted with hydrogens. Preferred reactantsare generically represented by the formula The production of bicyclo-The reaction of monoto di-ethylenically unsaturatedbicyclo(2.2.l)heptane and the acetylenic hydrocarbon is effected bymixing the reactants and nickel complex catalyst and maintaining themixture at a somewhat elevated reaction temperature until reaction iscomplete. Reaction temperatures from about 30 C. to about 250 C. aresatisfactory, although reaction temperatures from about 100 C. to about200 C. are preferred. While the condensation may be conducted atatmospheric pressure, it is generally desirable to employ pressures thatare super-atmospheric. Suitable reaction pressures vary from about 1 toabout 100 atmospheres. Particular advantage is taken of the pressuresgenerated when the reaction mixture is heated to reaction temperature ina sealed vessel, which pressures typically vary from about 2 to about 20atmospheres.

- The nickel complex is employed in catalytic amounts. Amounts of nickelcomplex catalyst from about 0.001% mole to about 5% mole based upon thelimiting reactant are suitable, although amounts of catalyst from about0.01% mole to about 1% mole on the same basis are preferred.

The reaction of monoto di-ethylenically unsaturatedbicyclo(2.2.1)heptane with acetylenic hydrocarbon results in theformation of monoto di-ethylenically unsaturated tricyclo (4.2.1.0)nonanes. The reaction is illustrated by the equation 0 ill C Theformation of the quadricyclic compound is favored by utilization ofhigher reaction temperatures and an excess amount of acetylenichydrocarbon relative to the amount of bicyclohep-tadiene, e.g., a molarratio of at least 2:1. Such quadricycloundecadienes, although alsonovel, are generally less preferred than the analogoustricyclononadienes, and in the reaction of bicycloheptadienes withacetylenic hydrocarbon, as well as in the reaction of bicycloheptenes,it is preferred to employ amounts of reactants that are substantiallyequimolar. A molar excess of the bicyclic reactant or a molar excess ofacetylenic hydrocarbon when bicycloheptenes are employed does not appearto be detrimental, although little advantage is gained by utilization ofsuch excesses and the use of substantially stoichiometric quantities ofreactants is pre ferred.

The quadricyclo(4.4.10 .0 ")undeca-3,8-diene is representative of aclass of compounds which, although less preferred, is within thecontemplated scope of the invention because of the presence within themolecule of the tricyclo(4.2.1.0 )non-3-ene ring system. Such compoundsare represented by the formula wherein R, R, m and n have the previouslystated significance, with the proviso that R substituents on the 7 and 8carbon atoms may together with the 7 and 8 carbon atoms form acarbocyclic ring system, preferably monocyclic, of from 4 to 7 carbonatoms, especially a cyclobutane or a cyclobutene ring. An additionalexample of this class of compounds is qu-adricyclo(4.4.1.0 .0 undecaneformed by hydrogenation of the quadricycloundecadiene by methodsdescribed hereinafter.

Regardless of the method of production, the monoto di-ethylenicallyunsaturated tricyclo(4.2.1.0 )nonanes are suitable for conversion to thecorresponding saturated compounds or compounds containing a lesserdegree of unsaturation by processes of hydrogenation. For example,tricyclo(4.2.1.0 )nona-3,7-dienes are converted to a mixture ofpartially saturated derivatives, e.g., a mixture of tri'cyclo(4.2.1.0)n0n-3-ene and tricyc1o(4.2.l.0 )non- 7-ene, by partial hydrogenation.Such a mixture is separated by conventional methods, e.g., distillation.By processes of complete hydrogenation, for example by allowinghydrogenation to proceed to completion, the nonadiene or either of theisomeric nonenes are converted to tricyclo(4.2.l.0 )nonanes.Hydrogenation is conveniently accomplished by contacting the unsaturatedtric'yclic compounds With molecular hydrogen in the presence of aconventional hydrogenation catalyst. Illustrative of such catalysts aretransition metals of Group VHI of the Periodic Table, e.g., nickel,platinum, palladium and rhodium or oxides thereof, which may beunsupported or supported on such inert carriers as carbon, alumina andthe like, as well as mixed oxide catalyst, e.g., copper chromite.

It is apparent from the above discussion that the processes of theinvention may be employed to produce a variety of saturated andunsaturated tricyclic compounds. The products of the invention, as wellas the reactants from which they are produced, are named in accord withconventional systems of naming and numbering polycyclic compounds. Thetricyclononanes, for example, are'numbered according to the followingsystem.

Typical of the products of the invention, numbered in this manner, are

Tricyclo (4.2.1 .0 nonane, Tricyclo (4.2. 1 .0 nona-3 ,7-diene,3,4-dimethyltetracyclo(4.2. 1 .0 non-3-ene, 7,8-diphenyltricyclo(4.2.1.0)nonane, 3 ,4,7,8-tetraphenyltricyclo(4.2.1 .0 non-7-ene,3-butyl-l-methyltricyclo(4.2.1.0 nona-3,7-diene, 9,9-dimethyltricyclo(4.2. 1.0 non-3-ene, 7-benzy1tricyclo(4.2.1.0 )non-7-ene,1,3,4-t1imethyltricyclo(4.2.0 nona-3,7-diene and the like.

The novel ring-unsaturated compounds are useful in a variety ofapplications as chemical intermediates. By employing the ethylenicunsaturation as reactive sites, the compounds of the invention may bepolymerized or co-polymerized with reactive unsaturates toformelastomers and thermoplastics. They are useful as ligands in theproduction of metal complexes, as dienophiles in Diels- Aldercondensations with many dienes, and additionally may be epoxidized toform useful epoxy resin precursors. The unsaturated linkages may behydrated or hydroxylated to form novel alcohols from which many usefulconventional derivatives may be produced. The saturated tri--cyclo(4.2.1.0 )nonanes of the invention find application as specialsolvents, e.g., in the field of coatings, and are also useful ascomponents of high energy fuels.

To further illustrate the novel processes of the invention and the novelproducts obtained thereby, the following examples are provided. Itshould be understood that they are not to be regarded as limitations, asthe teachings thereof may be varied as will be understood by one skilledin this art.

Example I Pentacyclo(8.2.1.1 .0 )tetradeca-5.11 diene (bicycloheptadienedimer), 20 g., was placed in a roundbottomed flask equipped with an 8cm. vacuum-jacketed reflux column having a water-cooled take-offcondenser and an ice bath-cooled receiver. The contents of the flaskwere maintained at 260-270 C. by heating in an oil bath. As the dimerrefluxed slowly, the pyrolysis products distilled from the reactionmixture and were collected in the receiver. When 9.8 g. of product hadbeen collected, the product mixture was analyzed and found to contain34.9% cyclopentadiene, 56.8% tricyclo(4.2.l.0 nona-3,7-diene, 7.3%bicyclo(4.2.1)nona-2,4,7-triene and 1% recovered bicycloheptadienedimer, all percentages being by weight. Distillation of the productmixture afforded separation of the tricyclo(4.2.1.0 )nona-3,7- diene,B.P. 78.5 C. at 106 mrn., n 1.4998, as a colorless liquid.

Analysis.Calc.: C, percent wt. 91.47; H, percent wt. 8.53. Found: C,percent wt. 91.49; H, percent wt. 8.57.

Mass spectroscopy indicated the product had a molecular weight of 118,and the nuclear magnetic resonance spectrum was consistent with theabove formula.

Example II Pentacyclo(8.2.1.1 .0 .0 )tetradeca-5,1l-diene(bicycloheptadiene dimer) was introduced at a constant rate along withhelium as a carrier gas, into a heated glass tube. A total of 7.4 g. ofthe dimer were introduced over a period of 70 minutes to a tube heatedto 400 C. The residence time in the tube was 0.16 minute. A liquidproduct was obtained, 7.2 g., which was shown by gasliquidchromatographic analysis to contain 6.1 millimole of tricyclo(4.2.1.0)non-3,7-diene, 26.7 millimoles of bicyclo(4.2.1)nona-2,4,7-triene, 31.6millimoles of cyclopentadiene and 6.6 millimoles recovered feed.

Example 111 Into an 84 ml. autoclave was introduced, under nitrogen,16.7 g. of bicyclo(2.2.1)-2-heptene, 16.7 g. of 2- butyne and 1.0 g. oftetrakis[tri(2-ethylhexyl)phosphite] nickel (0) as catalyst. Theresulting mixture was heated at 180l85 C. for 10 hours, during whichtime the pressure dropped from 190 p.s.i.g. to 40 p.s.i.g. Separationand gas-liquid chromatographic analysis of the 35.0 g. of liquid productindicated the presence of 6.81 g. unreacted Z-butyne, 2.49 g. ofbicycloheptadiene, 16.22 g. of 3,4-dimethyltricyclo (4.2.1.0 )non-3-eneand 8.39 g. of unidentified products. The products were obtained byfractional distillation, subsequent to removal of unreactedcyclopentadiene by distillation under reduced pressure at ambienttemperature, thereby preventing cyclopentadiene dimerization. The noveldimethyltricyclonene, 11 1.4836, distilled at C. at 100 mm. A massspectrogram of this product showed a molecular weight of 148, and thenuclear magnetic resonance spectrum was consistent with the aboveformula.

Example IV Into an 84 ml. autoclave was introduced, under nitrogen, 39.0g. of bicyclo(2.2.l)hepta-2,5-diene, 15.0 g. of diphenyl-acetylene and1.0 g. of tetrakis[tri(2-ethylhexyl) phosphiteJnickel (0). The reactionmixture was heated at 100 C. for 0.8 hour and at C. for 2 additionalhours. The product mixture was analyzed by gas-liquid chromatography andseparated by distillation to give 16.9 g. of a viscous, colorlessliquid, B.P. 172-3 C. at 2.6 mm., which represented a yield of 74%. Theproduct, 3,4-diphenyltricyclo (4.2.1.0 )nona-3,7-diene, was shown tohave a molecular weight of 270, and the nuclear magnetic resonancespectrum was consistent with a mixture of the endo and exo isomers ofthe above formula.

Example V A mixture of 10 g. of 2-butyne and 17 g. of bicyclo(2.2.1)hepta-2,5-diene were placed in an 84 ml. autoclave which wasequipped with a magnetic stirrer. After 1 g. of tetrakis[tri(Z-ethylhexyl)phosphite]nickel(0) was added, the mixture was heated at 70C. for 3.5 hours while the reaction mixture was stirred. The reactionproduct mixture was analyzed by gas-liquid chromatography and separatedby distillation under reduced pressure.

The product mixture contained 16.6 g. of 3,4-dimethyl tricyclo(4.2.1.0)nona-3,7-diene, a 1:1 addition product, 2.0 g. ofl,2,3,4-tetramethylbenzene and 1.1 g. of 3,4,8,9-tetramethylquadricyclo(4.4.1.0 .0 )undeca-3,8-diene, a product arisingfrom condensation of the acetylene and the bicycloheptadiene in a 2:1ratio. A mass spectrogram of the tricyclononadiene indicated a molecularweight of 146, and the nuclear magnetic resonance spectrum wasconsistent with a mixture of exo and endo isomers of the above formula.

Example VI The procedure of Example V was followed to react 20 g. of2-butyne with 15 g. of bicyclo(2.2.1)hepta-2,5- diene in the presence of1.5 g. of the same nickel catalyst at a temperature of 3 C. for 107minutes and an additional 37 minutes at 200 C. The recovered liquidproduct, 34.8 g. consisted of 20.7 g. of3,4,8,9-tetramethylquadricyclo(4.4.1.0 .0' )undeca-3,8-diene, 2.1 g. of1, 2,3,4-tetramethylbenzene, 1.2 g. of hexamethylbenzene, 0.9 g. ofunreacted 2-butyne and 9.9 g. of unidentified products, and a trace of3,4-dimethyltricyclo(4.2.1.0 nona-3,7-diene.

The tetramethylquadricycloundecadiene, n 1.5000- 1.5020, distilled :at103 C. at 8.5 mm. A mass spectrogram showed the molecular weight to be200, a c H compound, corresponding to a 2:1 condensation product ofZ-butyne and bicycloheptadiene. The nuclear magnetic resonance spectrumwas consistent with a mixture of exo and endo isomers of the aboveformula.

Example VII Under a variety of reaction conditions, l-butyne was reactedWith bicyclo(2.2.1)hepta-2,5-diene in the presence of nickel (0)catalysts. The reaction conditions, and the yield of3-ethyltricyclo(4.2.1.0 )nona-3,7-diene are shown in Table 1.

TABLE 1 Catalyst [(CflH50),POCH2]Z+2Ni [(ZethyllieXyl-OMPLNi Feed, g.:

8 15 10 20.0 15. 15. 0 C yst 1.0 1. 5 1.0 1.0 Reaction Conditions,G./min 15360/300 100-80/20 and 100-70/30 and 120-30/156 180/360.170-77/270. Recovered Feed:

l-butyne 3, 7 5. 8 Bicycloheptadiene 15. 9 9. 4 Product, g.:

Ethyl tricyclononadiene... 3. 2 1. 2 Diethylbenzenes 1. 6 3 0 ExampleVIII In an 84 ml. autoclave, 5.96 g. of tricyclo(4.2.l.0 nona-3,7-diene,B.P. 86 C. at 150 mm., n 1.5003, was hydrogenated at 50 C. and aninitial pressure of 830 p.s.i.g., using 0.2% Pd-on-charcoal catalyst.The hydrogen uptake was 0.105 millimole; theoretical uptake is 0.101millimole. The product, tricyclo(4.2.1.0 nonane, 11 1.4860, was acolorless liquid miscible with common organic solvents. The massspectrum confirmed a parent ion peak at 122.

The hydrogenation was repeated using a copper chromite catalyst at 150C. and 880 p.s.i.g. hydrogen pressure. The hydrogenation was terminatedbefore complete saturation, and a gas-liquid chromatographic analysis ofthe product mixture indicated the presence of three products, one ofwhich was the above-described tricyclo (4.2.1.0 )nonane. The tworemaining products were separated by a preparative gas-liquidchromatographic technique, and were each shown by mass spectroscopy tohave a molecular weight of 120. The two compounds were identified astricyclo(4.2.l.0 )non-3-ene and tricyclo(4.2.1.0 )non-7-ene, formed byhydrogenation of one of the double bonds in the original diene. Theretention of the tricyclo(4.2.l.0 ring structure was established byconversion of each compound to tricyclo(4.2. 1.0 )nonane upon furtherhydrogenation.

I claim as my invention:

1. The process for the production of monoto di-ethylenically unsaturatedtricyclo(4.2.1.0 )nonanes by reacting lbicyclo(2.2.1)heptane having from1 to 2 endo ethylenic linkages connecting non-bridgehead carbon atomsand having as the only non-hydrogen ring substituents from 0 to 6hydrocarbyl substituents independently having from 1 to carbon atoms,said hydrocarbyls having only aromatic unsaturation, with acetylenichydrocarbon having a single carbon-carbon triple bond, the onlynon-hydrogen substituents on which are hydrocarbyl having from 1 to 10carbon atoms and having only aromatic unsaturation, at a temperaturefrom about 30 C. to about 250 C. and a pressure from about 1 atmosphereto about 100 atmospheres, in the presence of a catalytic amount, saidamount being from about 0.01% mole to about 1% mole based on thelimiting reactant, of tetrakis(trihydrooarbylphosphite)nickel (0).

2. The process of claim 1 wherein thetetrakis(trihydrocarbylphosphite)nickel (0) istetr-akis[tri(2-ethylhexy1) phosphite]nickel (0).

3, The process for the production of tricyclo(4.2.l.0

nona-3,7-dienes by reacting bicyclo(2.2.1)hepta-2,5-diene withacetylenic hydrocarbon having a single carbon-carbon triple bond, theonly non-hydrogen substituents on which are hydrocarbyl having from 1 to6 carbon atoms and having only aromatic unsaturation, at a temperaturefrom about 30 C. to about 250 C. and a pressure from about 1 atmosphereto about atmospheres, in the presence ofa catalytic amount, said amountbeing from about 0.01% mole to about 1% mole based on the limitingreactant, of tetrakis[tri(2 ethylhexyl)phosphite] nickel (0).

4. The process of claim 3 wherein the acetylenic hydrooarbon is2-butyne.

5. The process for the production of tricyclo(4.2.1.0 non-3-enes byreacting bicyclo(2.2..1)hept-2-ene with acetylenic hydrocarbon having asingle carbon-carbon triple bond, the only non-hydrogen substituents onwhich are hydrocarbyl having from 1 to 6 carbon atoms and having onlyaromatic unsaturation, at a temperature from about 30 C. to about 250 C.and a pressure from about 1 atmosphere to about 100 atmospheres, in thepresence of a catalytic amount, said amount being from about 0.01% moleto about 1% mole based on the limiting reactant of tetrakis [tri2-ethylhexyl) phosphite] nickel (0) 6. The process of claim 5 whereinthe acetylenic hydrocarbon is phenylacetylene.

References Cited by the Examiner UNITED STATES PATENTS 2,686,208 8/1954Reed 260-666 2,928,865 3/ 1960 Brasen 260-666 2,940,984 6/1960Applequist 260-666 3,152,158 10/ 1964 Clark 260-666 FOREIGN PATENTS1,029,370 2/ 1958 Germany.

OTHER REFERENCES Bird et al., Chem. Ind., January 1960, pp. 20-21.

Bird et al., Tetrahedron Letters, No. 11, pp. 373-375 (1960).

Chemical Abstracts, vol. 57, July-December 1962, p. 25633.

Gerhard N. Schrauzer et al., Chem. Ber., vol. 97, pp. 2451-2462,September 1964.

DELBERT E. GANTZ, Primary Examiner.

V. OKEEFE, Assistant Examiner,

1. THE PROCESS FOR THE PRODUCTION OF MONO-TO DI-ETHYLENICALLYUNSATURATED TRICYCLO (4.2.1.0**2.5) NONANES BY REACTING BICYCLO (29291)HEPTANE HAVING FROM 1 TO 2 ENDO ETHYLENIC LINKAGES CONNECTINGNON-BRIDGEHEAD CARBON ATOMS AND HAVING AS THE ONLY NON-HYDROGEN RINGSUBSTITUENTS FROM 0 TO 6 HYDROCARBYL SUBSTITUENTS INDEPENDENTLY HAVINGFROM 1 TO 10 CARBON ATOMS, SAID HYDROCARBYLS HAVING ONLY AROMATICUNSATURATION, WITH ACETYLENIC HYDROCARBON HAVING A SINGLE CARBON-CARBONTRIPLE BOND, THE ONLY NON-HYDROGEN SUBSTITUENTS ON WHICH ARE HYDROCARBYLHAVING FROM 1 TO 10 CARBON ATOMS AND HAVING ONLY AROMATIC UNSATURATION,AT A TEMPERATURE FROM ABOUT 30* C. TO ABOUT 250*C. AND A PRESSURE FROMABOUT 1 ATMOSPHERE TO ABOUT 100 ATMOSPHERES, IN THE PRESENCE OF ACATALYTIC AMOUNT, SAID AMOUNT BEING FROM ABOUT 0.01% MOLE TO ABOUT 1%MOLE BASED ON THE LIMITING REACTANT, OF TETRAKIS(TRIHYDROCARBYLPHOSPHITE) NICKEN (0).